Stabilization of polyolefins with n, n-disubstituted glycine



United States Patent 3,335,108 STABILIZATION 0F POLYOLEFINS WITHN,N-DISUBSTITUTED GLYCINE Robert M. Pines, Spring Valley, N.Y., assignorto Geigy Chemical Corporation, Greenburgh, N.Y., a corporation ofDelaware No Drawing. Filed July 9, 1962, Ser. No. 208,599

Claims. (Cl. 26045.8)

This invention relates to the stabilization of polyolefin material, e.g.polypropylene, polyethylene, etc. against deterioration due tooxidation, heat, and/or light. The invention also relates tocompositions of said polyolefins stabilized thereby. The inventionfurther relates to novel synergistic combinations of stabilizers forsaid polyolefins.

Surprisingly it has now been found that polyolefins, in particularpolypropylene and high and low density polyethylene are stabilized withthe addition of small quantities of stabilizers of the Formula I /N A Bwherein A and B are each independently either hydroxy-loweralkyl orcarboxy-lower-alkyl, and the alkali metal, e.g. sodium, potassium orammonium salts of I.

Examples of compounds of the Formula I are: N,N-di(2hydroxyethyl)-glycine, N,N di(carboxymethyl)- glycine, N-2-hydroxyethyl -N-carboxymethyl-glycine.

While the stabilizers of the Formula I are contemplated for use inpolyolefins, it is desirable to use the same not alone, but rather incombination with other thermal and/or oxidative deterioration inhibitingstabilizers. When a stabilizer of the Formula I is used in conjunctionwith such stabilizers there is sometimes observed a synergistic effectin protecting the polyolefin resin against deterioration due to heat andoxidation. Thus, the stabilizers of the Formula I often remarkablyincrease the life of the resin as well.

The stabilizers of the Formula I are used generally in an amount of fromabout 0.01% by weight to about 5% by weight based upon the stabilizedcomposition. Those auxiliary stabilizers which are also present in theresin which is stabilized besides those of the Formula I may be found inamounts from about 0.05% to about 5% by weight in preferred embodimentsof the invention.

It has now been found that the stabilizers of Formula I are especiallyvaluable for use in stabilizing polyolefin compositions, e.g.polypropylene or polyethylene, when such stabilizers of the Formula Iare used in combination with other additives, such as thermal andoxidative stabilizers having phenolic groups therein. For example theauxiliary stabilizers of the invention are represented by compounds ofthe Formula II:

wherein R and R each independently respresent an alkyl group of from 1to 18 carbon atoms, e.g. methyl, ethyl, propyl, butyl, pentyl, octyl,dodecyl, octadecyl, etc., a cycloalkyl group having 5 or 6 carbon atoms,e.g. cyclopentyl or cyclohexyl, a phenyl group, an alkylphenyl group offrom 7 to 24 carbon atoms, e.g. methylphenyl, ethylphenyl, butylphenyl,octylphenyl, octa- Patented Aug. 8, 1967 decylphenyl, dimethylphenyl,dibutylphenyl, dioctadecylphenyl, etc., carbalkoxyalkyl of 3 to 15carbon atoms, e.g. carbomethoxymethyl, carbethoxyethyl, carbobutoxyethyl, carbo-n-lauryloxyethyl, etc. or carbalkoxyphenyl of 8 to19 carbon atoms, e.g. carbomethoxyphenyl, carbethoxyphenyl,carbo-n-octyloxyphenyl, carbo-n-lauryloxyphenyl, etc., alkylthioalkyl,

R is defined the same as R and also the same as R R representsalkylhydroxyphenyl of 7 to 24 carbon atoms, e.g. methylhydroxyphenyl,ethylhydroxyphenyl, butylhydroxyphenyl, octylhydroxyphenyl,octadecylhydroxyphenyl, di-t-butylhydroxyphenyl,methyl-di-tbutylhydroxyphenyl, etc.,

X, Y and Z are each independently O, S, imino, substituted imino, e.g.benzyl, alkanoyl, lower alkyl, etc.

Examples of compounds according to the Formula II which are usefullyemployed in combination with compounds of the Formula I are:

6- (4-hydroxy-3 ,5 -di-t-butylanilino -2,4-bis- (n-octylthio1,3,5-triazine,

6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-bis-phenylthio- 1,3 ,5-triazine,

6- 4-hydroxy-3,S-di-t-butylanilino-2,4-bisoctadecylthio)-l,3,5-triazine,

2-n-ocLylthio-4,6-bis- 4-hydroxy-3 ,5 -di-t-butylphenoxy 1,3,S-triazine,

6- 4-hydroxy-3,S-di-t-butylphenoxy) -2,4-bisnoctylthio l ,3 ,5-triazine,

6- (4-hydroxy-3,5-di-t-butylphenoxy -2,4-bisn-octylthioethylthio) 1 ,3,5 -triazine,

6- (4-hydroxy-3 ,5 -di-t-buty-lanilino -2,4-bis-cyclohexyl thio-1,3 ,5-triazine,

6- 2-hydroxy-3 ,5 -di-t-butyl-6-methylanilino -2,4-

bisn-o ctylthio l ,3 ,5 -triazine,

6- 4-hydroxy-3 ,5 -di-t-butylanilino -2,4-bis- 2,3-

dimethylphenylthio l ,3,5 -triazine,

6- (4-hydroxy-3 ,5 -di-t-butylanilino) -2,4-biscarbo-nlauryloxyethylthio-1 ,3 ,5 -triazine,

6- 4-hydroxy-3 ,5 -di-t-butylanilino -2,4-bis-( 4-toctylphenoxy) -1 ,3,5 -triazi ne,

6- 4-hydroxy-3 ,5 -di-t-butylanilino) -2,4-bis-2-carbo-nlauryloxyphenylthio 1 ,3 ,5 -triazine,

6- 4-hydroxy-3,5-di-t-butyl-N-benzylanilino -2,4-bis- (n-octylthio) -1,3,5 -triazine.

wherein R is hydroxyl; alkylphenoxy, preferably having from 7 to 24carbon atoms; phenyl; phenoxyl; alkylthio or alkoxy, preferablyalkylthio or alkoxy having from 12 to 24 carbon atoms, examples ofuseful alkoxy groups represented by R being methoxy, ethoxy, isopropoxy,propoxy, butoxy, secondary butoxy, tertiary butoxy, pentoxy, hexoxy,heptoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy,octadecyloxy, nonadecyloxy, heneicosoxy, docosoxy, tricosoxy,tetracosoxy, etc.; in the foregoing examples for R it is understood thatoxygen may be usefully substituted by sulfur so that methylthio,ethylthio, isopropylthio, propylthio, butylthio, sec. butylthio,t-butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio,decylthio, undecylthio, dodecylthio, tridecylthio, tetradecylthio,pentadecylthio, hexadecylthio, heptadecyl- 3 thio, octadecylthio, etc.are also contemplated; examples of useful alkylphenoxy groupsrepresented by R being methylphenoxy, ethylphenoxy, isopropylphenoxy,propylphenoxy, butylphenoxy, dibutylphenoxy, tribut'ylphenoxy,pentylphenoxy, hexylphenoxy,

heptylphenoxy, octylphenoxy, nonylphenoxy, decylphenoxy, undecylphenoxy,dodecylphenoxy, tridecylphenoxy, tetradecylphenoxy, pentadecylphenoxy,hexadecylphenoxy, heptadecylphenoxy, octadecylphenoxy, dinonylphenoxy,etc.; alkylthioalkyloxy; alkylthioalkylthio;

R is defined the same as R above, except that R is not phenyl, norhydroxyl;

R and R each independently represents alkyl, e.g. alkyl having from 1 to18 carbon atoms, preferably having from 1 to 5 carbon atoms, especiallytertiary butyl; examples of useful alkyl groups being methyl, ethyl,propyl, isopropyl, butyl, secondary butyl, tertiary butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc.;

R represents hydrogen or lower alkyl, e.g. methyl, ethyl, propyl,isopropyl, butyl, secondary butyl, tertiary butyl, pentyl, hexyl, butespecially methyl; and

n represents 0, 1, 2 or 3, preferably 0 or 1.

In general, it has been found that the stabilizers of the Formula I arevaluable in enhancing the stabilization effect of a wide variety ofstabilizers for polyolefinic material. This enhancement is surprisinglygreater than would be predicted from the stabilization realized by eachstabilizer taken alone. Thus, often where a stabilizer having a phenolicresidue, especially a phenolic residue substituted in at least one ofthe positions ortho to the phenolic OH group is used in conjunction witha stabilizer of the Formula I, a remarkably synergistic stabilizersystem is obtained. The foregoing Formulae II and III are illustrativeof two classes of stabilizers having a phenolic residue therein. Thescope of the invention, however, extends beyond these two classes toinclude any phenolic residue containing stabilizer suitable for thestabilization of polyolefinic material, especially polypropylene. Theinvention also extends to the use of other stabilizers such as themercapto acids of the Formula V hereinbelow.

Compounds of the Formula II are prepared according to methods describedin copending application Ser. No. 87,520, filed Feb. 21, 1961, by M.Dexter et al., now abandoned.

Compounds of the Formula III are prepared according to methods describedin copending application Ser. No. 102,958, filed Apr. 14, 1961, by I. D.Spivack, now abandoned.

Examples of further phenolic stabilizers are those of the Formula IV:

wherein Ra (IV) B represent an alkylene group (straight or branchedchain), as defined for A above, except that when R is hydrogen inFormula I, then B may contain up to 24 carbon atoms, especially from 6to 18 carbon atoms;

11 represents 1 or 2;

m represents 0 or 1; and

R represents (a) whennis 1:

(i) hydrogen, or

(ii) alkylthioespecially having from 1 to 24 carbon atoms (preferablyhaving from 8 to 18 carbon atoms), or

(iii) hydroxyalkylthioespecially hydroxyethylthio;

and

(b) when n is 2:

(i) alkylenethio, preferably alkylenethio having from 1 to 6 carbonatoms, especially alkylenethio having 2 carbon atoms, or

(ii) alkyleneespecially as defined for A above, or

(iii) alkyleneoxyespecially alkyleneoxy having 2 carbon atoms.

Preparation of the compounds of the Formula IV is disclosed in copendingapplication, Ser. No. 164,618, filed Jan. 5, 1962, by Martin Dexter etal., now abandoned.

Other stabilizers may also be usefully employed in conjunction with thestabilizers of the Formula I, such as for example stabilizers of theFormula V wherein R and R are each independently an alkyl group of from1 to 24 carbon atoms, such as for example the compound methyl, ethyl,propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl.

It is an object of the invention to provide stabilized compositions ofpolypropylene which are normally solid at room temperature. It isanother object of the invention to provide a method of stabilizingnormally solid poly propylene by incorporating therein a minor portion,preferably from about 0.01% to about 10% (based on the totalcomposition) of a stabilizing system which comprises a stabilizer of theFormula I in an amount of from about 0.01% to about 5% by weight and, ina preferred embodiment, at least one other stabilizer as describedabove. Other additives and stabilizers may also be present withoutadversely affecting the aforesaid stabilizing system.

Solid polymers of polyolefins, e.g. polypropylene, find extensive use invarious forms of plastic ware. Many different articles of manufactureare produced from polypropylene plastic materials which can be moldedand shaped at higher temperatures while remaining relatively rigid atordinary room temperature. Polyethylene thermoplastic molding or coatingagents have high dielectric strength and excellent resistance to water,but unfortunately they are prone to attack by atmospheric oxidationand/0r exposure to light, e.g. UV light. Moreover, during processing,such thermoplastic materials are subject to polymeric degradation due tothermal instability. Deterioration caused by one or more of theforegoing may lead to loss, e.g. of dielectric properties, and/or todiscoloration, embrittlement or other physical break-down.

The present invention presents a solution to the problem of how to checkthese deteriorating agencies and enhance the appearance of the solidpolypropylene and While the present stabilizer system employs a compoundof Formula I as a basic component, surprisingly in many cases, saidsystem goes far beyond the expected stabilizing power of said compoundof Formula I alone. Compositions comprising polypropylene and saidcompound of Formula I alone, for example, possess far less stability tothermal oxidation than polypropylene resins stabilized with a systemaccording to the present invention comprising a compound of the FormulaI and at least one other stabilizer, e.g. II, HI, IV or V. Moreover, thesuperior results obtained cannot be explained as a mere additive elfect.When the system of the invention is employed as a stablizing system forpolypropylene, a surprisingly high increase in ageing life andprocessing stability at elevated temperatures, is obtained. It isentirely unexpected that the improvement in stability characteristics ofthe polypropylene is significantly greater than the improvement realizedwhen each of the individu- 211 components of the stabilizer system isemployed alone ,pnder the same conditions. The improvement from thecombined stabilizer system is far greater than the sum of the individualimprovements due to the single stabilizer components when employed alonein the polypropylene; thus, a true synergism is produced.

Any olefinic polymer, but especially polypropylene and polyethylene,which is normally solid at ordinary room temperature may be stabilizedwith the system according to the invention.

Thus, besides homop-olymeric material, the method of the invention isuseful for stabilizing copolymers, including block and graft polymersand physical mixtures thereof.

The stabilizer system of the invention may be incorporated intopolypropylene during milling, extruding, or any other suitable process.Moreover, said stabilizer system may be advantageously preformed beforeincorporation into the solid polymer. Alternatively, the individualcomponents of the stabilizer system may be incorporated into thepolypropylene separately or in combination with one or several, othercomponents, Concentrations of from about 0.01%. to about 10% by weightof the total stabilizer system, based upon the total stabilizedcomposition, are advantageously employed according to the invention.

The following examples of stabilization of polyolefinic material, egpolypropylene and polyethylene, are meant for illustration purposes andare not intended to limit the scope of the invention in any way. In saidexamples parts are by weight unless otherwise specified and. therelationship of parts by weight to parts by volume is as that of gramsto cubic centimeters. Temperatures are expressed in degrees centigrade.

In addition to the foregoing auxiliary stabilizers, it is understoodthat other additives, or coloring agents may be present in the polymericmaterial to be stabilized. For example, there may be present pigments,dyes, light stabilizers, lubricants, plasticizing agents, anti-slipagents, thermal stabilizers, antioxidants.

Further, the auxiliary stabilizers used in combination with thecompounds of the Formula I, may be any suitable stabilizer having thegroup wherein R may be hydrogen or alkyl, especially alkyl from 1 to 12carbon atoms, R may be alkyl, especially alkyl having from 1 to 12 5carbon atoms; examples of alkyl for R and R being methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,wherein normal or branched chain alkyl groups are contemplated.

Specific auxiliary stabilizers having the group are 1 EXAMPLES:STABILIZATION OF POLYPROPYLENE Example 1 Unstabilized polypropylenepowder (Hercules PROFAX 6501) is thoroughly blended with 0.1% by weightof N,N-bis(carboxymethyl)-glycine and 0.1% by weight of 6-(4hydroxy-3,S-di-t-butylanilino)-2,4-bis-(noctylthio)-1,3,5-triazine. Theblended material thereafter is milled on a two roller mill at 182 forsix minutes, after which time the stabilized polypropylene is sheetedfrom the mill and allowed to cool.

The milled polypropylene sheet, thus stabilized, is then cut into smallpieces and pressed for seven minutes on a hydraulic press at 218 and 174pounds per square inch pressure. The resultant sheet of 25 mil thicknessis then tested for resistance to accelerated aging in a forced draftover at 149. The stabilized polypropylene is not subject todeterioration after 40 hours in the oven while the unstabilized materialdeteriorates after about 3 hours; polypropylene is stabilized withN,N-bis(carboxymethyl)- glycine alone for less than 7 hours; with 0.1%of 6-(4- hydroxy 3,5 di t butylanilino)-2,4-bis-(n-octylthio)1,3,5-triazine alone polypropylene fails after 110 hours. Atelevatedtemperatures, for example about 300", the so stabilizedpolypropylene exhibits very good processing stability and very littlepolymer degradation as compared to the unstabilized polypropylene.

If in the foregoing Example 1, the concentrations of the individualstabilizer components each are varied within the stabilizer system sothat concentrations of 0.05%, 0.1%, 0.3%, 0.5%, and 1% by weight,respectively, are

employed, then in a similar fashion good results are obtained.

If in the foregoing Example 1, in place of 0.1% of 6-(4-hydroxy 3,5-dit-butylanilino) 2,4-bis-(n octylthio)-1,3,5-triazine, a similar amountof one of the following is substituted: 6- 4-hydroxy-3 ,5-di-t-butylanilino -2,4-bis-pheny1thio- 1,3,5-tn'azine, 6- (4-hydroxy-3,5 ,-di-t-butylanilino) -2,4-bisoctadecylthio)-l,3,5-triazine, 6-(4-hydroxy-3 ,5 ,di-t-butylanilino)-2,4-bis-cyclohexylthio-1,3,5-triazine, 6- 2-hydroxy-3 ,5-di-t-butyl-G-methylanilino) -2,4-bis- (n-octylthio)-1,3,5-triazine,

6- (4-hydroxy-3 ,5 -di-t-butylanilino) -2,4-bis-(2,3-dimethylphenylthio) 1,3 ,5 -triazine,

6-(4-hydroxy-3,S-di-t-butylanilino)-2,4-bis-(carbo-nlauryloxyethylthio)-1,3,5-t1iazine,

6- (4-hydroxy-3,S-di-t-butylanilino) -2,4-bis- (4-t-octylphenoxy) -1,3,5 -triazine,

6- (4-hydroxy-3 ,5 -di-t-butylanilino -2,4-bis-(2-carbo-nlauryloxyphenylthio) -1,3 ,5 -triazine,

6- (4-hydroxy-3 ,5 -di-t-butyl-N-benzylanilino) -2,4-bis-(nocty1tl1io)-1,3 ,5 -triazine,

4,6-bis- (4-hydroxy-3 ,5 -di-t-butylphenoxy) -2- (n-octylthio) -1,3 ,5-triazine,

then similar results are obtained.

Example 2 In the same manner as in Example 1 polypropylene is stabilizedwith a stabilizer system comprising 0.1% ofN,N-bis(carboxymethyl)glycine and 0.1% ofdi-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate (weightpercent).

The so-stabilized polypropylene is tested in the same manner as inExample 1 and is stabilized against deterioration for 60 hours. Theunstabilized polypropylene deteriorates after only 3 hours, while when0.1% by weight alone ofdi-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate is used, thestabilization is not effective after 30 hours. Similarly, it 0.1% byweight of N,N-bis (carboxymethyl)-glycine alone is used, then the samefails in 7 hours.

In a similar way, if instead of 0.1% by Weight of din-octaclecyl3,5-di-t-butyl-4 hydroxybenzylphosphonate one of the followingstabilizers is employed in the same amount:

Di-n-octadecyl- (3 -t-butyl-4-hydroxy-S-methylb enzyl) phosphonate,

Di-n-octadecyl- (3 ',5 -di-t-butyl-4'-hydroxyphenyl) ethane-phosphonate,

Di-n-octadecy1-3,S-di-t-butyl-Z-hydroxybenzylphosphonate,

Di-n-dodecyl-Z- (3 ,5'-di-t-butyl-4'-hydroxyphenyl) -ethane phosphonate,

Diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate,

Dimethyl-3 ,5 -di-t-butyl-4-hydroxybenzylphosphonate,

Di-p-t-octylphenyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate,

O-n-butyl-3 ,5 -di-t-butyl-4-hydroxybenzylphosphonic acid,

Di-n-dodecyl-3,S-di-t-butyl-4-hydrovybenzylphosphonate,

Di-n-dodecyl-3,5-di-t-butyl-4-hydroxylbenzylphosphonate,

O-n-decyl-O-phenyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate,

S,S-di-n-octadecyl-3,5-di-tbutyl-4-hydroxybenzyldithiophosphonate,

O-n-octadecyl- (3 -di-t-butyl-4-hydroxyb enzyl) -benzenephosphinate,

then similar results are obtained.

Example 3 In the same manner as in Example 1, stable polyproylenecompositions are prepared with 0.1% by weight ofN,N-bis(carboxymethyl)-glycine and 0.5% by Weight of each one of thefollowing compounds, taken singly: n-octadecyl-B- 35-di-t-butyl-4-hydroxyphenyl) -propionate anddilauryl-thio-dipropionate.

Example 4 In the same manner as in Example 1, stable compositions ofpolypropylene are prepared with 0.1% by weight of6-(4-hydroxy-3,5-di-t-butylanilino) 2,4-bis-(n-octylthio)-1,3,5-triazineand 0.1% by weight of sodium-N,N- di(2-hy.droxyethyl) glycine etc.

What is claimed is:

1. A composition comprising a member selected from the group consistingof polypropylene and polyethylene, from about 0.01% to about 0.5% ofN,N-bis(carboxymethyl) glycine and from about 0.1% to about 0.5 of atleast one member selected from the group consisting of6-(4-hydroxy-3,S-di-t-butylanilino) 2,4-bis-(n-octylthio)-1,3,5-triazine; 2-(n-octylthio)-4,6-bis(4-hydroxy-3,5-dit-butylphenoxy)-1,3,5 triazine; di-(n-octadecyl) 4hydroxy-3,S-di-t-butylbenzylphosphonate; and n-octadecylfl-(4-h-ydroxy3,5 di-t-butylphenyl)propionate, all percentages based on weight oftotal composition.

2. A composition comprising polypropylene, from about 0.01% to about 0.5of N,N-bis(carboxymethyl) glycine and from about 0.1% to about 0.5% of6-(4- hydroxy-3,S-di-t-butylanilino)-2,4-bis (n-octylthio) 1,3,5-triazi11e, all percentages based on weight of total composition.

3. A composition comprising polypropylene, from about 0.01% to about 0.5of N,N-bis(carboxymethyl) glycine and from about 0.1% to about 0.5% of2-(11- octylthio) 4,6 bis (4-hydroxy-3,S-dLt-butylphenoxy)-1,3,5-triazine, all percentages based on weight of total composition.

4. A composition comprising polypropylene, from about 0.01% to about 0.5of N,N-bis(carboxymethyl) glycine and from about 0.1% to about 0.5% ofdi-(noctadecyl) 4-hydroxy-3,4-di-t butylbenzylphosphonate, allpercentages based on weight of total composition.

5. A composition comprising polypropylene, from about 0.01% to about 0.5of N,N-bis(carboxymethyl) glycine and from about 0.1% to about 0.5% ofn-octadecyl-fl-(4-hydroxy 3,S-di-t-butylphenyl)proprionate, allpercentages based on weight of total composition.

References Cited UNITED STATES PATENTS 2,428,353 10/1947 BerWorth260-534 2,667,522 1/1954 McElroy 26045.85 2,985,617 5/1961 Salyer et a1.26045.85 3,017,422. 5/1962 Thompson 260-4595 3,102,107 8/1963 Soeder26045.85

DONALD E. CZAJA, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

H. E. TAYLOR, Assistant Examiner.

1. A COMPOSITION COMPRISING A MEMBER SELECTED FROM THE GROUP CONSISTINGOF POLYPROPYLENE AND POLYETHYLENE, FROM ABOUT 0.01% TO ABOUT 0.5% OF N,NBIS (CARBOXYMETHYL) GLYCINE AND FROM ABOUT 0.1% TO ABOUT 0.5% OF ATLEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF6-(4-HYDROXY-3,5-DI-T-BUTYLANILINO)-2,4-BIS-(N-OCTYLTHIO)1,3,5-TRIAZINE;2-(N-OCTYLTHIO)-4,6-BIS-(4-HYDROXY-3,5-DIT-BUTYLPHENOXY)-1,3,5-TRIAZINE;DI-(N-OCTADECYL)-4-HYDROXY-3,5-DI-T-BUTYLBENZYLPHOSPHONATE; ANDN-OCTADECYLB-(4-HYDROXY-3,5-DI-T-BUTYLPHENYL) PROPIONATE, ALLPERCENTAGES BASED ON WEIGHT OF TOTAL COMPOSITION.